Abstract
Exfoliated graphitic carbon nitride (g-C3N4) and two commercially available nanomaterials from titanium dioxide (P25 and CG300) were tested for the photocatalytic degradation of paracetamol (PAR), ibuprofen (IBU), and diclofenac (DIC). Prior to photocatalytic experiments, the nanomaterials were characterized by common methods, such as X-ray diffraction (XRD), UV–VIS diffuse reflectance spectroscopy (DRS), Fourier transformed infrared spectroscopy in attenuated total reflection mode (FTIR–ATR), transmission electron microscopy (TEM), physisorption of nitrogen, and dynamic vapor adsorption (DVS) of water. The sizes and specific surface area (SSA) of the TiO2 nanoparticles were 6 nm and 300 m2·g−1 for CG300 and 21 nm and 50 m2·g−1 for P25. The SSA of g-C3N4 was 140 m2·g−1. All photocatalytic experiments were performed under UV (368 nm), as well as VIS (446 nm) irradiation. TiO2 P25 was the most active photocatalyst under UV irradiation and g-C3N4 was the most active one under VIS irradiation. Photodegradation yields were evaluated by means of high performance liquid chromatography (HPLC) and reaction intermediates were identified using gas chromatography with mass detection (GC–MS). Paracetamol and ibuprofen were totally removed but the intermediates of diclofenac were observed even after 6 h of irradiation. Some intermediates, such as carbazole-1-acetic acid, 2,6-dichloraniline, and hydroxylated derivates of diclofenac were identified. This study showed that g-C3N4 is a promising photocatalyst for the degradation of pharmaceuticals in an aqueous environment, under visible light.
Highlights
The utilization of pharmaceutical products has been continually increasing all over the world
Melamine for the preparation of g-C3N4, paracetamol, diclofenac sodium salt, ibuprofen, and chloroacetic acid were purchased from Sigma-Aldrich (Darmstadt, Germany)
Photocatalytic degradations are supposed to be based on the reactions of hydroxyl radicals formed by complex reactions of photoinduced electrons and holes (h) with oxygen, water, and hydroxide ions [60,61,62,63], as follows: h+ + H2O → OH + H+, (3)
Summary
The utilization of pharmaceutical products has been continually increasing all over the world. The presence of pharmaceuticals and their metabolites in water is beginning to be a serious problem for humans and animals [1,2,3,4,5,6,7] These compounds get to waterbodies from various sources, such as disposals from hospitals and households, excretions by humans and animals, and it is important to develop new and effective technologies for their removal from wastewaters and the whole aquatic ecosystem. Among the groups of pharmaceuticals, non-steroidal, anti-inflammatory drugs are widely used and, are widely present in waterbodies. Their typical representatives are diclofenac, paracetamol, and ibuprofen; these compositions were photocatalytically degraded in TiO2 suspensions in some studies [20,21,22,23,24,25]
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